KR20170005788A - Electroconductive particles, conductive material, and connection structure - Google Patents

Abstract

Provided is a conductive particle capable of effectively increasing conduction reliability between electrodes when the electrodes are electrically connected. The conductive particle according to the present invention comprises base particles and a conductive portion disposed on the surface of the base particle, wherein a compression modulus at a load of 3 mN is not less than 5000 N / mm2 and not more than 30000 N / mm2, s is calculated to be 0.8 or more and 1.6 or less when measured at a load of 3 mN (expression: repulsion energy = displacement m at a load of 3 mN x 3 mN x compression recovery rate at a load of 3 mN).

Description

ELECTROCONDUCTIVE PARTICLES, CONDUCTIVE MATERIAL, AND CONNECTION STRUCTURE [0002]

The present invention relates to a conductive particle in which a conductive portion is disposed on a surface of a base particle. The present invention also relates to a conductive material and a connection structure using the conductive particles.

Anisotropic conductive paste such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, a plurality of conductive particles are dispersed in the binder resin.

The anisotropic conductive material can be used for various connection structures, for example, connection (FOG (Film on Glass)) between a flexible printed board and a glass substrate, connection (COF (Chip on Film)) between a semiconductor chip and a flexible printed board, (COG (Chip on Glass)) between a semiconductor chip and a glass substrate and connection (FOB (Film on Board)) between a flexible printed substrate and a glass epoxy substrate.

For example, when an electrode of a semiconductor chip and an electrode of a glass substrate are electrically connected by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is arranged on a glass substrate. Then, the semiconductor chips are laminated and heated and pressed. Thereby, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.

As an example of the conductive particles, Patent Document 1 below discloses polymer particles and conductive particles having a conductive metal layer on the surface of the polymer particles. The fracture point load of the polymer particles is 9.8 mN (1.0 gf) or less. Further, in Patent Document 1, it is described that the 10% K value of the polymer particles may be 7350 N / mm 2 (750 kgf / mm 2) to 49000 N / mm 2 (5000 kgf / mm 2).

WO2012 / 020799 A1

In the case of using a conventional conductive particle as described in Patent Document 1 to obtain a connection structure by connecting the electrodes therebetween, initial connection resistance may be increased or conduction reliability may be lowered. For example, when the connection structure is exposed to the conditions of 85 캜 and 85% humidity for 500 hours, the connection resistance between the electrodes may be increased, and the reliability of conduction may be low.

Also, in recent years, miniaturization of electronic parts has been progressing. Thus, in the wiring connected by the conductive particles in the electronic component, the L / S representing the width of the line L in which the wiring is formed and the width of the space S in which no wiring is formed is reduced . In the case where such fine wiring is formed, it is difficult to secure sufficient conduction reliability by conducting the conductive connection using the conventional conductive particles.

An object of the present invention is to provide a conductive particle capable of effectively increasing the reliability of conduction between electrodes when the electrodes are electrically connected.

It is also an object of the present invention to provide a conductive material and a connection structure using the conductive particles.

According to a broad aspect of the present invention, there is provided a base material comprising base particles and a conductive portion disposed on a surface of the base particle, wherein the base material has a compressive modulus at the time of 3 mN load of not less than 5000 N / mm2 and not more than 30000 N / s at a load of 3 mN is 0.8 or more and 1.6 or less.

Rebound energy = 3 mN x 3 mN displacement at the time of loading 占 퐉 x 3 mN Compression recovery rate at load%

In a specific aspect of the conductive particles according to the present invention, the base particles are resin particles or organic-inorganic hybrid particles.

In a specific aspect of the conductive particles according to the present invention, the conductive particles have projections on the outer surface of the conductive portion.

In a specific aspect of the conductive particles according to the present invention, the conductive particles have an insulating material disposed on the outer surface of the conductive portion.

According to a broad aspect of the present invention, there is provided a conductive material comprising the above-mentioned conductive particles and a binder resin.

According to a broad aspect of the present invention, there is provided a communication device including a first connection object member, a second connection object member, a first connection object member, and a connection portion connecting the second connection object member, A connection structure formed by one conductive particle or formed by a conductive material containing the conductive particles and a binder resin is provided.

In the conductive particle according to the present invention, the conductive part is disposed on the surface of the base particles, and the compressive modulus at the time of 3 mN load is not less than 5000 N / mm 2 and not more than 30000 N / mm 2, Since the repulsive energy is not less than 0.8 and not more than 1.6, when the electrodes are electrically connected by using the conductive particles according to the present invention, the reliability of conduction between the electrodes can be effectively increased.

1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.
2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.
4 is a front sectional view schematically showing a connection structure using conductive particles according to a first embodiment of the present invention.

Hereinafter, the details of the present invention will be described. In the present specification, "(meth) acryl" means one or both of "acrylic" and "methacrylic", and "(meth) acrylate" means one of "acrylate" and "methacrylate" It means both.

(Conductive particles)

The conductive particles according to the present invention include base particles and conductive portions disposed on the surface of the base particles.

In the conductive particle according to the present invention, the compressive modulus at the time of 3 mN load is not less than 5000 N / mm 2 and not more than 30000 N / mm 2. In the conductive particles according to the present invention, the repulsive energy determined from the following equation at a compression rate of 0.33 mN / s at 3 mN load is 0.8 or more and 1.6 or less.

Rebound energy = 3 mN x 3 mN displacement at the time of loading 占 퐉 x 3 mN Compression recovery rate at load%

The conductive particles according to the present invention exhibit relatively hard and low repulsive energy. The conductive particles according to the present invention have novel properties that are not conventionally provided.

In the present invention, since the above-described structure is provided, when the electrodes are electrically connected using the conductive particles according to the present invention, the reliability of conduction between the electrodes can be effectively increased. For example, with respect to the connection structure in which the electrodes are electrically connected to each other using the conductive particles according to the present invention, when the connection structure is exposed to the conditions of 85 ° C and 85% humidity for 500 hours, the connection resistance between the electrodes is increased Can be suppressed.

The reason why the above-described effects are exhibited is that increase in the resistance value due to springback of the conductive particles is suppressed when the connection target members such as the semiconductor chip and the glass substrate are thin.

In addition, since the conductive particles according to the present invention are relatively hard, indentations suitable for the electrodes can be formed after the conductive connection. Also by this, the initial connection resistance can be lowered and the conduction reliability can be improved.

From the viewpoint of further lowering the connection resistance and further enhancing the conduction reliability between the electrodes, the compression modulus (K value) of the conductive particles at a load of 3 mN is preferably 7000 N / mm 2 or more, more preferably 9000 N / Mm 2 or more, preferably 25000 N / mm 2 or less, and more preferably 20,000 N / mm 2 or less.

The repulsive energy of the conductive particles is preferably 0.9 or more, more preferably 1.0 or more, preferably 1.5 or less, more preferably 1.4 or less, more preferably 1.5 or less, from the viewpoint of further lowering the connection resistance and further improving the conduction reliability between the electrodes. Or less.

The displacement at 3 mN load in the conductive particle and the compressive elastic modulus at 3 mN load in the conductive particle can be measured as follows.

One conductive particle is compressed under a condition of loading a test load of 90 mN at 25 占 폚 at a maximum test load of 90 mN on the flattened indenter end face of a cylindrical column (diameter 50 占 퐉, made of diamond) using a micro compression tester. At this time, the load value N and the compression displacement (mm) are measured. From the obtained measured values, the above-described compressive modulus can be obtained by the following formula. As the micro compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Co., Ltd. or the like is used.

K value (N / mm 2) = (3/2 ^1/2 ) · F · S ^-3/2 · R ^-1/2

F: Load value, 0.003 (N)

S: Compressive displacement (mm) when conductive particles are compressed to 3 mN

R: radius of conductive particle (mm)

The compressive modulus shows the hardness of the conductive particles in a universal and quantitative manner. By using the compressive elastic modulus, the hardness of the conductive particles can be quantitatively and univocally expressed.

The compression recovery rate for obtaining the repulsive energy can be measured as follows.

The conductive particles are sprayed on the sample surface. One conductive particle to be sprayed was subjected to a 3 mN load (inversion) of the conductive particle at 25 캜 at the flat end surface of a cylindrical column (diameter of 100 탆, made of diamond) Load value). Thereafter, the load is reduced to the original point load value (0.40 mN). And the compression-recovery rate can be obtained from the following equation by measuring the load-compression displacement between them. The load speed is 0.33 mN / sec. As the micro compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Co., Ltd. or the like is used.

Compression recovery rate (%) = [(L1-L2) / L1] 100

L1: Compressive displacement from the original point load value to the reverse load value when the load is applied

L2: Deflection displacement from the inverse load value when releasing the load to the original point load value

Particles which are comparatively hard and exhibit a low rebound energy, such as the conductive particles according to the present invention, can be obtained by appropriately adjusting the polymerization conditions of the base particles and the hardness of the conductive portion.

Regarding the base particles, for example, when the base particles are inorganic particles or organic-inorganic hybrid particles except for the metal described later, by adjusting the condensation reaction conditions, the oxygen partial pressure at the time of firing, the firing temperature and the firing time, During the condensation reaction, the radical polymerization reaction can be performed in the firing step while suppressing the radical polymerization reaction. As a result, the base particles can be obtained which can obtain the conductive particles which are relatively hard and exhibit low repulsion energy.

Regarding the conductive portion, by appropriately adjusting the thickness of the metal species and the conductive portion which are the material of the conductive portion, the physical properties of the conductive particles can be obtained in addition to the physical properties of the base particles and the desired repulsive energy properties.

Examples of the metal species include nickel, nickel alloys, nickel boron alloys, nickel, alloys of boron and tungsten, and combinations thereof, which are preferable examples of materials containing nickel.

Hereinafter, the present invention will be described in detail with reference to the drawings. The present invention is not limited to the following embodiments, and the following embodiments may be appropriately modified, improved, or the like so long as the features of the present invention are not impaired.

1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.

The conductive particles 1 shown in Fig. 1 have base particles 2 and conductive portions 3. Fig. The conductive part 3 is disposed on the surface of the base particle 2. In the first embodiment, the conductive portion 3 is in contact with the surface of the base particle 2. The conductive particles (1) are coated particles in which the surface of the base particles (2) is covered with the conductive parts (3). In the conductive particle 1, the conductive portion 3 is a single conductive portion (conductive layer).

Unlike the conductive particles 11 and 21 to be described later, the conductive particles 1 do not have a core material. The conductive particles 1 do not have projections on the conductive surface and do not have projections on the outer surface of the conductive portion 3. [ The conductive particles (1) are spherical.

As described above, the conductive particles according to the present invention may not have protrusions on the conductive surface, may not have protrusions on the outer surface of the conductive portion, or may be spherical. Unlike the conductive particles 11 and 21 to be described later, the conductive particles 1 do not have an insulating material. However, the conductive particles (1) may have an insulating material disposed on the outer surface of the conductive part (3).

2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.

The conductive particles 11 shown in Fig. 2 have base particles 2, conductive portions 12, a plurality of core materials 13, and a plurality of insulating materials 14. The conductive part 12 is disposed on the surface of the base particle 2 so as to be in contact with the base particle 2. In the conductive particle 11, the conductive portion 12 is a conductive portion (conductive layer) of a single layer.

The conductive particles 11 have a plurality of projections 11a on the conductive surface. In the conductive particle 11, the conductive portion 12 has a plurality of projections 12a on its outer surface. A plurality of core materials (13) are disposed on the surface of the base particles (2). A plurality of core materials (13) are embedded in the conductive part (12). The core material 13 is disposed inside the projections 11a and 12a. The conductive portion 12 covers a plurality of core materials 13. The outer surfaces of the conductive parts 12 are raised by the plurality of core materials 13 to form the projections 11a and 12a.

The conductive particles (11) have an insulating material (14) disposed on the outer surface of the conductive part (12). At least a part of the outer surface of the conductive part 12 is covered with the insulating material 14. [ The insulating material 14 is formed of a material having an insulating property and is insulating particles. As described above, the conductive particles according to the present invention may have an insulating material disposed on the outer surface of the conductive portion. However, the conductive particles according to the present invention may not necessarily contain an insulating material.

3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.

The conductive particles 21 shown in Fig. 3 have base particles 2, conductive portions 22, a plurality of core materials 13, and a plurality of insulating materials 14. The conductive portion 22 has a first conductive portion 22A on the base particle 2 side and a second conductive portion 22B on the opposite side of the base particle 2 side.

The conductive particles (11) and the conductive particles (21) differ only in conductive portions. That is, in the conductive particles 11, the first conductive portions 22A and the second conductive portions 22B are formed in a two-layered structure. The first conductive portion 22A and the second conductive portion 22B are formed as different conductive portions.

The first conductive portion 22A is disposed on the surface of the base particle 2. A first conductive portion 22A is disposed between the base particle 2 and the second conductive portion 22B. The first conductive portion 22A is in contact with the base particle 2. Therefore, the first conductive portion 22A is disposed on the surface of the base particle 2, and the second conductive portion 22B is disposed on the surface of the first conductive portion 22A. The conductive particles 21 have a plurality of projections 21a on the conductive surface. In the conductive particles 21, the conductive portion 22 has a plurality of projections 22a on its outer surface. The first conductive portion 22A has a protrusion 22Aa on its outer surface. The second conductive portion 22B has a plurality of projections 22Ba on its outer surface. In the conductive particles 21, the conductive portions 22 are two conductive portions (conductive layers).

Hereinafter, other details of the conductive particles will be described.

[Substrate Particle]

Examples of the base particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles and metal particles. The base particles may be core shell particles having a core and a shell disposed on the surface of the core. The core may be an organic core. The shell may be an inorganic shell. Among them, base particles excluding metal particles are preferable, and resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles are more preferable. Particularly preferred are resin particles or organic-inorganic hybrid particles in that the effect of the present invention is further improved.

The base particles are preferably resin particles formed by a resin. When connecting the electrodes using the conductive particles, the conductive particles are disposed between the electrodes, and then pressed to compress the conductive particles. When the base particles are resin particles, the conductive particles are liable to be deformed at the time of pressing, and the contact area between the conductive particles and the electrode is increased. As a result, the reliability of conduction between the electrodes increases.

As the resin for forming the resin particles, various organic materials are suitably used. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; But are not limited to, polyalkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, Various polymerizable monomers having an epoxy resin, an unsaturated polyester resin, a saturated polyester resin, a polysulfone, a polyphenylene oxide, a polyacetal, a polyimide, a polyamideimide, a polyetheretherketone, a polyether sulfone and an ethylenic unsaturated group And polymers obtained by polymerization of one kind or two or more kinds. The hardness of the base particles can be easily controlled within a suitable range. Therefore, the resin for forming the resin particles is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.

When the resin particle is obtained by polymerizing a monomer having an ethylenic unsaturated group, examples of the monomer having an ethylenic unsaturated group include a monomer which is incompatible with the monomer and a monomer which is crosslinkable.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and? -Methylstyrene; Carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylates such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate; Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; Acid vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene.

Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di Polyfunctional (meth) acrylates such as (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate; (Meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, trimethylolpropane trimethoxysilane, triallyl trimellitate, divinyl benzene, diallyl phthalate, diallyl acrylamide, diallyl ether, , Silane-containing monomers such as vinyltrimethoxysilane, and the like.

The above-mentioned resin particles can be obtained by polymerizing the above-mentioned polymerizable monomer having an ethylenic unsaturated group by a known method. Examples of the method include suspension polymerization in the presence of, for example, a radical polymerization initiator, and polymerization by swelling the monomer together with the radical polymerization initiator using uncrosslinked seed particles.

When the base particles are inorganic particles other than metals or organic-inorganic hybrid particles, examples of inorganic substances for forming base particles include silica and carbon black. The particles formed by the silica are not particularly limited. For example, particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and then firing if necessary, . Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

In the case where the base particles are metal particles, silver, copper, nickel, silicon, gold, titanium and the like can be given as a metal which is a material of the metal particles. However, the base particles are preferably not metal particles, and are preferably not copper particles.

The particle diameter of the base particles is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 1000 μm or less, More preferably not more than 500 mu m, further preferably not more than 50 mu m, further preferably not more than 30 mu m, particularly preferably not more than 5 mu m, and most preferably not more than 3 mu m. When the particle diameter of the base particles is not less than the above lower limit, the contact area between the conductive particles and the electrode is increased, so that the reliability of the connection between the electrodes is further increased, and the connection resistance between the electrodes connected via the conductive particles is further lowered. Further, when the conductive part is formed on the surface of the base particles by electroless plating, it is difficult to coagulate and the coagulated conductive particles are hardly formed. When the particle diameter of the base particles is less than the upper limit, the conductive particles are easily compressed sufficiently, the connection resistance between the electrodes is further lowered, and the interval between the electrodes is further reduced.

The particle diameter of the base particles indicates a diameter when base particles are spherical, and indicates a maximum diameter when base particles are not spherical.

Particularly preferably, the particle size of the base particles is 1 탆 or more and 5 탆 or less. If the particle diameter of the base particles is in the range of 1 to 5 占 퐉, the distance between the electrodes becomes small, and even if the thickness of the conductive part is increased, small conductive particles can be obtained.

[Conductive part]

The metal for forming the conductive part is not particularly limited. Examples of the metal include gold, silver, palladium, ruthenium, rhodium, osmium, iridium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, , Germanium, cadmium, silicon, and alloys thereof. Examples of the metal include indium tin oxide (ITO) and solder. Among them, an alloy including tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable because connection resistance between electrodes can be further lowered.

Like the conductive particles 1 and 11, the conductive portion may be formed by one layer. Like the conductive particles 21, the conductive portion may be formed by a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers. When the conductive part is formed by a plurality of layers, the outermost layer is preferably an alloy layer including a gold layer, a nickel layer, a palladium layer, a copper layer, or a tin and silver layer, more preferably a gold layer. When the outermost layer is the preferable conductive layer, the connection resistance between the electrodes is further lowered. Further, when the outermost layer is a gold layer, corrosion resistance is further increased.

The method of forming the conductive portion on the surface of the base particles is not particularly limited. Examples of the method of forming the conductive portion include a method of electroless plating, a method of electroplating, a method of physical vapor deposition, and a method of coating a paste containing metal powder or metal powder and a binder on the surface of base particles And the like. Among them, the electroless plating method is preferable because the formation of the conductive part is simple. Examples of the physical deposition method include vacuum deposition, ion plating and ion sputtering.

The particle diameter of the conductive particles is preferably 0.5 占 퐉 or more, more preferably 1 占 퐉 or more, preferably 520 占 퐉 or less, more preferably 500 占 퐉 or less, still more preferably 100 占 퐉 or less, Is not more than 50 mu m, particularly preferably not more than 20 mu m. When the particle diameters of the conductive particles are not less than the lower limit and not more than the upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large when the electrodes are connected using the conductive particles, and when the conductive particles are formed, . Further, the distance between the electrodes connected via the conductive particles does not become excessively large, and the conductive portion becomes difficult to peel off from the surface of the base particles. When the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the conductive particles can be suitably used for the conductive material.

The particle diameter of the conductive particles means the diameter when the conductive particles are spherical, and the maximum diameter when the conductive particles have shapes other than the spheroidal shape.

The thickness of the conductive portion (the thickness of the entire conductive portion) is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 10 탆 or less, more preferably 1 탆 or less, further preferably 0.5 탆 or less , Particularly preferably not more than 0.3 mu m. The thickness of the conductive portion is the total thickness of the conductive layer when the conductive portion has multiple layers. When the thickness of the conductive portion is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained and the conductive particles are not excessively hardened, and the conductive particles are sufficiently deformed at the time of connection between the electrodes.

When the conductive portion is formed by a plurality of layers, the thickness of the conductive layer in the outermost layer is preferably 0.001 탆 or more, more preferably 0.01 탆 or more, preferably 0.5 탆 or less, more preferably 0.1 Mu m or less. When the thickness of the conductive layer of the outermost layer is not less than the lower limit and not more than the upper limit, the coating by the conductive layer of the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes becomes further lower. Further, when the outermost layer is a gold layer, the thinner the thickness of the gold layer, the lower the cost.

The thickness of the conductive portion can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).

From the viewpoint of effectively increasing the conductivity, it is preferable that the conductive particles have a conductive portion including nickel. The content of nickel in 100 wt% of the conductive portion including nickel is preferably 50 wt% or more, more preferably 65 wt% or more, still more preferably 70 wt% or more, still more preferably 75 wt% More preferably 80% by weight or more, particularly preferably 85% by weight or more, and most preferably 90% by weight or more. The content of nickel in 100 wt% of the conductive portion including nickel is preferably 100 wt% or less, 99 wt% or less, or 95 wt% or less. If the nickel content is lower than the lower limit described above, the connection resistance between the electrodes is further lowered. In addition, when the oxide film on the surface of the electrode or the conductive part is small, the connection resistance between the electrodes tends to decrease as the content of nickel increases.

As a method for measuring the content of the metal contained in the conductive portion, various known analytical methods can be used without particular limitation. As the measuring method, an absorption analysis method or a spectrum analysis method can be mentioned. In the above absorption spectrophotometry, a frame absorption spectrophotometer, an electric heating spectrophotometer, or the like can be used. Examples of the spectrum analysis include plasma emission analysis and plasma ion mass spectrometry.

When measuring the average content of the metal contained in the conductive portion, it is preferable to use an ICP emission spectrometer. Commercially available products of the ICP emission spectrometer include ICP emission spectrometers manufactured by HORIBA.

The conductive portion may contain phosphorus or boron in addition to nickel. In addition, the conductive portion may include a metal other than nickel. In the conductive portion, when a plurality of metals are included, a plurality of metals may be alloyed.

The content of phosphorus or boron in 100 wt% of the conductive portion including nickel and phosphorus or boron is preferably 0.1 wt% or more, more preferably 1 wt% or more, preferably 10 wt% or less, more preferably 5 By weight or less. If the content of phosphorus or boron is less than the lower limit and the upper limit, the resistance of the conductive part is further lowered, and the conductive part contributes to reduction of the connection resistance.

[Core material]

It is preferable that the conductive particles have protrusions on the conductive surface. The conductive particles preferably have protrusions on the outer surface of the conductive portion. It is preferable that the projections are plural. In many cases, an oxide film is formed on the surface of the electrode connected by the conductive particles. In many cases, an oxide film is formed on the surface of the conductive part of the conductive particles. By using the conductive particles having the protrusions, the conductive particles are arranged between the electrodes, and then the conductive particles are pressed, whereby the oxide film is effectively removed by the protrusions. As a result, the electrode and the conductive particle can be brought into contact more reliably, and the connection resistance between the electrodes can be lowered. In the case where the conductive particles have an insulating material on the surface or the conductive particles are dispersed in the binder resin and can be used as a conductive material, the resin between the conductive particles and the electrode is effectively removed by the protrusions of the conductive particles . As a result, the reliability of conduction between the electrodes is further enhanced.

Since the core material is embedded in the conductive portion, it is easy to make the conductive portion have a plurality of protrusions on the outer surface. However, in order to form protrusions on the conductive surface of the conductive particles and the surface of the conductive portion, the core material may not necessarily be used.

Examples of the method for forming the projections include a method of attaching a core material to the surface of base particles and then forming a conductive part by electroless plating; a method of forming a conductive part by electroless plating on the surface of base particles, A method of forming a conductive portion by electroless plating and a method of adding a core material in a step of forming a conductive portion by electroless plating on the surface of base particles.

Examples of the material of the core material include a conductive material and a non-conductive material. Examples of the conductive material include metals, oxides of metals, conductive base metals such as graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene and the like. Examples of the non-conductive material include silica, alumina, barium titanate, and zirconia. Among them, a metal is preferable because the conductivity can be increased and the connection resistance can be effectively lowered. The core material is preferably a metal particle. As the metal material of the core material, a metal exemplified as the material of the conductive material can be suitably used.

The shape of the core material is not particularly limited. The shape of the core material is preferably massive. As the core material, for example, a lump of particles, an agglomerated mass aggregating a plurality of minute particles, and a lump of an amorphous substance can be given.

The average diameter (average particle diameter) of the core material is preferably 0.001 탆 or more, more preferably 0.05 탆 or more, preferably 0.9 탆 or less, and more preferably 0.2 탆 or less. If the average diameter of the core material is above the lower limit and below the upper limit, the connection resistance between the electrodes is effectively lowered.

The " average diameter (average particle diameter) " of the core material indicates a number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 pieces of any core material with an electron microscope or an optical microscope and calculating an average value.

The number of the projections per one conductive particle is preferably 3 or more, and more preferably 5 or more. The upper limit of the number of the projections is not particularly limited. The upper limit of the number of the projections can be appropriately selected in consideration of the particle diameter of the conductive particles and the like.

The average height of the plurality of projections is preferably 0.001 탆 or more, more preferably 0.05 탆 or more, preferably 0.9 탆 or less, and more preferably 0.2 탆 or less. When the average height of the projections is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes is effectively lowered.

[Insulating material]

The conductive particles preferably include an insulating material disposed on an outer surface of the conductive portion. In this case, when the conductive particles are used for connection between the electrodes, it is possible to further prevent short-circuiting between adjacent electrodes. Specifically, when a plurality of conductive particles are brought into contact with each other, an insulating material exists between a plurality of electrodes, so that a short circuit between the electrodes adjacent to each other in the transverse direction can be prevented not between the upper and lower electrodes. Further, when connecting the electrodes, the conductive particles of the conductive particles and the insulating material between the electrodes can be easily excluded by pressing the conductive particles with the two electrodes. When the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, the insulating material between the conductive portion of the conductive particles and the electrode can be more easily excluded.

It is preferable that the insulating material is insulating particles in that the insulating material can be more easily excluded when the electrodes are compressed.

Specific examples of the insulating resin that is the material of the insulating material include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, crosslinked products of thermoplastic resins, thermoplastic resins, thermosetting resins and water- .

The average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles and the use of the conductive particles. The average diameter (average particle diameter) of the insulating material is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 1 탆 or less, and more preferably 0.5 탆 or less. When the average diameter of the insulating material is not less than the lower limit, conductive portions of the plurality of conductive particles are less likely to come into contact with each other when the conductive particles are dispersed in the binder resin. When the average diameter of the insulating particles is less than the upper limit, since the insulating material between the electrodes and the conductive particles is removed at the time of connection between the electrodes, there is no need to excessively increase the pressure and there is no need to heat at a high temperature.

The " average diameter (average particle diameter) " of the insulating material indicates a number average diameter (number average particle diameter). The average diameter of the insulating material is obtained by using a particle size distribution measuring device or the like.

(Conductive material)

The conductive material according to the present invention includes the above-described conductive particles and a binder resin. The conductive particles are preferably dispersed in the binder resin and can be used as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive particles and the conductive material are preferably used for electrical connection between the electrodes, respectively. The conductive material is preferably a circuit connecting material.

The binder resin is not particularly limited. As the binder resin, a known insulating resin is used.

Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer and an elastomer. The binder resin may be used alone or in combination of two or more.

Examples of the vinyl resin include vinyl acetate resin, acrylic resin and styrene resin. Examples of the thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer and a polyamide resin. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin and an unsaturated polyester resin. The curable resin may be a room-temperature curable resin, a thermosetting resin, a photo-curable resin, or a moisture-curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a hydrogenated product of a styrene-isoprene- Additives and the like. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

The conductive material and the binder resin preferably include a thermoplastic component or a thermosetting component. The conductive material and the binder resin may include a thermoplastic component or may include a thermosetting component. The conductive material and the binder resin preferably include a thermosetting component. The thermosetting component preferably includes a curing compound that can be cured by heating and a thermosetting agent. The curable compound that can be cured by the heating and the thermosetting agent are used at a proper blending ratio so that the binder resin is cured.

The conductive material may contain, in addition to the conductive particles and the binder resin, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, Flame retardant, and the like.

The conductive material may be used as a conductive paste and a conductive film. When the conductive material is a conductive film, a film not containing conductive particles may be laminated on the conductive film containing conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

The content of the binder resin in 100 wt% of the conductive material is preferably 10 wt% or more, more preferably 30 wt% or more, still more preferably 50 wt% or more, particularly preferably 70 wt% Is 99.99% by weight or less, and more preferably 99.9% by weight or less. When the content of the binder resin is not less than the lower limit and not more than the upper limit, the conductive particles are efficiently arranged between the electrodes, and the conduction reliability of the member to be connected connected by the conductive material is further enhanced.

The content of the conductive particles in 100 wt% of the conductive material is preferably 0.01 wt% or more, more preferably 0.1 wt% or more, preferably 40 wt% or less, more preferably 20 wt% or less, Is not more than 10% by weight. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, the reliability of conduction between the electrodes is further increased.

(Connection structure)

The connection structure can be obtained by using the conductive particles or by connecting the members to be connected using a conductive material including the conductive particles and a binder resin.

Wherein the connection structure includes a first connection object member, a second connection object member, and a connection portion connecting the first and second connection object members, and the connection portion is formed by the conductive particles of the present invention, Or a connection structure formed by a conductive material including the conductive particles and a binder resin. When conductive particles are used, the connection itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.

4 is a front sectional view schematically showing a connection structure using conductive particles according to a first embodiment of the present invention.

The connecting structure 51 shown in Fig. 4 has a connecting member 51 connecting the first connection target member 52, the second connection target member 53 and the first and second connection target members 52 and 53 54). The connection portion 54 is formed by curing a conductive material containing the conductive particles 1. [ In Fig. 4, the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, the conductive particles 11 and 21 may be used.

The first connection target member 52 has a plurality of first electrodes 52a on its surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on its surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected to each other by one or more conductive particles 1. [ Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1. [

The manufacturing method of the connection structure is not particularly limited. As an example of a manufacturing method of the connection structure, there is a method in which the conductive material is disposed between the first connection target member and the second connection target member and a laminate is obtained and then the laminate is heated and pressed have. The pressure of the pressurization is about 9.8 x 10 ⁴ to 4.9 x 10 ⁶ Pa. The temperature of the heating is about 120 to 220 占 폚.

Specific examples of the member to be connected include electronic parts such as semiconductor chips, capacitors and diodes, and electronic parts such as printed boards, flexible printed boards, glass epoxy boards and circuit boards such as glass boards. The connection target member is preferably an electronic component. The conductive particles are preferably used for electrical connection of electrodes in electronic parts.

Examples of the electrode provided on the member to be connected include a metal electrode such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection target member is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of the metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The present invention is not limited to the following examples.

(Example 1)

300 g of 0.13 wt% aqueous ammonia solution was placed in a 500 mL reaction vessel equipped with a stirrer and a thermometer. Then, 3.8 g of methyltrimethoxysilane, 10.8 g of vinyltrimethoxysilane, 0.2 g of a silicone alkoxy oligomer A ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd., Weight average molecular weight having an epoxy group and an alkyl group directly bonded to a silicon atom: about 1600) was added slowly. After the hydrolysis and condensation reaction proceeded with stirring, 1.6 mL of a 25 wt% aqueous ammonia solution was added, and the particles were isolated from the aqueous ammonia solution. The resulting particles were subjected to an oxygen partial pressure of 10 ^-10 atm at 450 DEG C And fired for 2 hours (firing time) to obtain organic-inorganic hybrid particles (base particles). The obtained organic-inorganic hybrid particles had a particle diameter of 3.00 mu m.

Using the obtained organic-inorganic hybrid particles, a nickel layer was formed on the surface of the organic-inorganic hybrid particles by an electroless plating method. The thickness of the nickel layer was 0.10 탆.

(Examples 2 to 5)

The conditions of the manufacturing method of the conductive particles of Example 1 were changed to the conditions of Table 2 and organic-inorganic hybrid particles were prepared and the physical property values described in the following Table 1 were used, 2 to 5 conductive particles were obtained.

(Example 6)

Base particles similar to those of Example 1 were prepared. 10 parts by weight of the base particles were dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution by using an ultrasonic dispersing machine, and then the solution was filtered to take out base particles. Subsequently, the base particles were added to 100 parts by weight of a 1 wt% solution of dimethylamine borane to activate the surface of the base particles. The surface-activated base particles were sufficiently washed with water and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension. Subsequently, 1 g of metallic nickel particle slurry (average particle diameter 100 nm) was added to the above dispersion for 3 minutes to obtain base particles with the core material adhered thereto. The base material with the core material attached thereto was added to 500 parts by weight of distilled water and dispersed to obtain a suspension. Conductive particles were obtained in the same manner as in Example 1 except that the base particles were changed to the base particles to which the core material was adhered and the physical property values were set forth in Table 1 below.

(Example 7)

In a 1000 mL separable flask equipped with a four-neck separable cover, a stirrer, a three-way cock, a cooling tube and a temperature probe, 100 mmol of methyl methacrylate and 100 mmol of N, N, N-trimethyl- A monomer composition containing 1 mmol of ethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride was weighed in ion-exchanged water to a solid content of 5% by weight, stirred at 200 rpm, The polymerization was carried out at 70 캜 for 24 hours in a nitrogen atmosphere. After completion of the reaction, the resultant was lyophilized to obtain an insulating particle having an average particle diameter of 220 nm and a CV value of 10%, having an ammonium group on its surface.

The insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.

10 g of the conductive particles obtained in Example 6 were dispersed in 500 ml of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. Filtered through a mesh filter of 0.3 mu m, washed with methanol, and dried to obtain conductive particles having insulating particles adhered thereto.

As a result of observation by a scanning electron microscope (SEM), only one coating layer composed of insulating particles was formed on the surface of the conductive particles. The coated area of the insulating particles (i.e., the projected area of the particle diameter of the insulating particles) with respect to the area of 2.5 mu m from the center of the conductive particles was calculated by image analysis, and the coverage was 40%.

(Example 8)

Conductive particles were obtained in the same manner as in Example 1, except that the particle diameter of the organic-inorganic hybrid particles was changed to 2.25 占 퐉 and the physical properties shown in Table 1 below were used.

(Example 9)

Conductive particles were obtained in the same manner as in Example 1 except that methyltrimethoxysilane was changed to phenyltrimethoxysilane at the time of production of the organic-inorganic hybrid particles and the physical properties shown in Table 1 below were used.

(Example 10)

In producing the organic-inorganic hybrid particles, the silicon alkoxy oligomer A was changed to a silicon alkoxy oligomer B (KR-513, manufactured by Shin-Etsu Chemical Co., Ltd.) having an organic substituent group methyl / acryloyl group and an alkoxy group methoxy group, Conductive particles were obtained in the same manner as in Example 1 except that the physical properties shown in Table 1 were used.

(Comparative Example 1)

804 parts by weight of ion-exchanged water, 1.2 parts by weight of 25% ammonia water, and 336.6 parts by weight of methanol were placed in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and 3-methacryloxypropyl tri A mixed solution of 80 parts by weight of methoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) and 59.4 parts by weight of methanol was added to conduct hydrolysis and condensation reaction of 3-methacryloxypropyltrimethoxysilane to obtain a methacryloyl group (Polymerizable polysiloxane particles) was prepared. After 2 hours from the start of the reaction, the emulsion of the obtained polysiloxane particles was sampled and the particle diameter was measured to find that the particle diameter was 2.25 占 퐉.

Subsequently, a solution obtained by dissolving 2 parts by weight of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium salt ("Hytenol (registered trademark) NF-08" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier in 80 parts by weight of ion- , 56 parts by weight of cyanuric acid triallyl (TAC) and 1.6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) , And emulsified and dispersed to prepare an emulsion of the monomer component.

The resulting emulsion was added to the emulsion of the polymerizable polysiloxane particles and stirred again. After one hour from the addition of the emulsion, the mixed solution was sampled and observed under a microscope. As a result, it was confirmed that the polymerizable polysiloxane particles absorbed the monomer and became non-enlarged.

Subsequently, 8 parts by weight of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium salt and 20.6 parts by weight of ion-exchanged water were added. The temperature of the reaction solution was raised to 65 캜 in a nitrogen atmosphere, Radical polymerization of the monomer components was carried out. After the radical polymerization, the emulsion was subjected to solid-liquid separation, and the obtained cake was washed with ion-exchanged water and methanol, and then dried at 120 캜 for 2 hours under vacuum to obtain base particles as polymer particles. The obtained base particles had a particle diameter of 3.00 mu m.

Conductive particles were obtained in the same manner as in Example 1 except that the base particles were used.

(Comparative Example 2)

680 parts by weight of ion-exchanged water, 1.2 parts by weight of 25% ammonia water, and 520 parts by weight of methanol were placed in a four-necked flask equipped with a cooling tube, a thermometer and a dropping funnel. And 60 parts by weight of vinyltrimethoxysilane ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.), which is a crosslinkable silane-based monomer, was dropped thereinto. After maintaining the internal temperature at 25 캜 for 15 minutes, polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium salt , 32 parts by weight of a 20% aqueous solution of polyvinyl alcohol (" Hytenol NF-08 " manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for another 15 minutes to hydrolyze and condense the vinyltrimethoxysilane, To prepare an emulsion of particles (polymerizable polysiloxane particles). The emulsion of the obtained polysiloxane particles was sampled and the particle diameter was measured to find that the particle diameter was 2.25 占 퐉.

Subsequently, to a solution obtained by dissolving 1.0 part by weight of a 20% aqueous solution of polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium salt ("Hytenol NF-08" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier in 42 parts by weight of ion-exchanged water, DVB960 24 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V- 65 "), and the resulting mixture was emulsified and dispersed at 8000 rpm for 5 minutes by a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a monomer emulsion. This monomer emulsion was added to the emulsion of the polysiloxane particles and stirred again. One hour after the addition of the monomer emulsion, the reaction solution was sampled and observed under a microscope. As a result, it was confirmed that the specific polysiloxane particles absorbed the monomer composition and became non-enlarged.

Subsequently, the reaction solution was heated to 65 占 폚 in a nitrogen atmosphere and maintained at 65 占 폚 for 2 hours to carry out radical polymerization. After cooling the reaction solution, the obtained emulsion was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and then with methanol, dried at 120 ° C for 2 hours, and further heat-treated at 350 ° C for 3 hours in a nitrogen atmosphere Thereby obtaining base particles which are polymer particles. The obtained base particles had a particle diameter of 3.00 mu m.

(evaluation)

(1) compression modulus (K value) at 3 mN load, displacement at 3 mN load and compression recovery rate

The compressive elastic modulus (K value) of the conductive particles at 3 mN load, the displacement of the conductive particles at 3 mN load, and the compressive recovery rate of the conductive particles were measured at 23 deg. C by the method described above. The repulsive energy was calculated from the displacement of the conductive particles at 3 mN load and the compression recovery rate of the conductive particles.

(2) the state of indentation

Fabrication of the connection structure:

, 10 parts by weight of an epoxy compound as a thermosetting compound ("EP-3300P" manufactured by Nagase ChemteX Corp.) and 10 parts by weight of an epoxy compound as a thermosetting compound (EPICLON HP-4032D, manufactured by DIC) , 5 parts by weight of a thermal cation generator as a curing agent ("SI-60" manufactured by Sanshin Chemical Industries, Ltd.) and 10 parts by weight of a polyvinyl butyral resin And 20 parts by weight of silica (average particle diameter: 0.25 mu m) as a filler were added. The resulting conductive particles were added in an amount of 10% by weight in 100% by weight of the mixture, and then stirred at 2000 rpm for 5 minutes using a planetary stirrer Thereby obtaining an anisotropic conductive paste.

A glass substrate having an Al-Ti 4% electrode pattern (Al-Ti 4% electrode thickness 1 占 퐉) having L / S of 20 占 퐉 / 20 占 퐉 on the upper surface was prepared. Further, a semiconductor chip having a gold electrode pattern (gold electrode thickness of 20 占 퐉) having L / S of 20 占 퐉 / 20 占 퐉 was prepared.

Anisotropic conductive paste immediately after preparation was coated on the upper surface of the glass substrate to a thickness of 20 占 퐉 to form an anisotropic conductive material layer. Then, the semiconductor chips were laminated on the upper surface of the anisotropic conductive material layer so that the electrodes were opposed to each other. Thereafter, while the temperature of the head was adjusted so that the temperature of the anisotropic conductive material layer was 170 占 폚, a pressure heating head was placed on the upper surface of the semiconductor chip, a pressure of 2.5 MPa was applied, To obtain a connection structure.

Using a differential interference microscope, the electrode provided on the glass substrate was observed from the glass substrate side of the obtained connecting structure, and the presence or absence of the indentation of the electrode with which the conductive particles were contacted was observed. The indentation state was determined based on the following criteria.

[Judgment Criteria of Indentation Condition]

○○○: Before the reliability test (initial), there are 0 points where the particle indentation is not clearly visible in 50 bumps. After performing the reliability test, there are 0 points where the particle indentation of the 50 bumps is not clearly visible

○○: Before the reliability test (initial), there are 0 points where the particle indentation is not clearly displayed in 50 bumps. After the reliability test, the number of points where the indentation of particles in the 50 bumps is not clearly visible is less than 5 points

○: Before the reliability test (initial), there are 0 points where the particle indentation does not clearly appear in 50 bumps. After the reliability test, the points where the indentation of particles in the 50 bumps are not clear are 5 points or more and 10 points or less

△: Prior to the reliability test (initial), the number of points where the particle indentation does not clearly appear in 50 bumps is 1 point or more and less than 5 points

占: Prior to the reliability test (initial), there were 5 points or more where the particle indentations of 50 bumps were not clearly displayed

The reliability test means that the connection structure is exposed for 500 hours at a temperature of 85 캜 and a humidity of 85%.

(3) Initial connection resistance A

Measurement of connection resistance:

The connection resistance A between the opposing electrodes of the connection structure obtained by (2) evaluation of the presence or absence of indentation formation was measured by the four-terminal method. The initial connection resistance A was determined based on the following criteria.

[Evaluation Criteria of Initial Connection Resistance A]

○ ○ ○: Connection resistance A is 2.0Ω or less

○○: Connection resistance A is more than 2.0Ω and less than 3.0Ω

: Connection resistance A is more than 3.0? 5.0?

?: Connection resistance A is more than 5.0? 10?

X: Connection resistance A exceeds 10 Ω

(4) Connection resistance (long-term reliability) after 500 hours exposure to 85 ° C and 85%

The connection structure obtained by (2) evaluation of the presence or absence of indentation formation was left under the conditions of 85 캜 and 85% humidity for 500 hours. In the connection structure after being left standing, the connection resistance B between the electrodes facing the connection structure was measured by the four-terminal method. The connection resistance after 500 hours exposure to the conditions of 85 캜 and 85% humidity was determined based on the following criteria.

[Evaluation Criteria of Connection Resistance after 500-hour Exposure to 85 ° C and 85% RH]

X: Connection resistance B is less than 1 times of connection resistance A

○ ○: Connection resistance B is more than 1 times and less than 1.5 times of connection resistance A.

O: The connection resistance B is 1.5 times or more and less than twice the connection resistance A

DELTA: Connection resistance B is at least 2 times and less than 5 times of connection resistance A

X: The connection resistance B is 5 times or more the connection resistance A

The results are shown in Tables 1 and 2 below.

1: conductive particles
2: Base particles
3:
11: conductive particles
11a:
12:
12a:
13: core material
14: Insulating material
21: conductive particles
21a:
22:
22a:
22A: first conductive part
22Aa:

Claims (6)

Comprising a base particle and a conductive portion disposed on a surface of the base particle,
The compression modulus at the time of 3 mN load is not less than 5000 N / mm < 2 > and not more than 30000 N /
Wherein a repulsive energy determined from the following equation at a compression rate of 0.33 mN / s at a load of 3 mN is 0.8 or more and 1.6 or less.
Rebound energy = 3 mN x 3 mN displacement at the time of loading 占 퐉 x 3 mN Compression recovery rate at load% The conductive particle according to claim 1, wherein the base particles are resin particles or organic-inorganic hybrid particles. The conductive particle according to claim 1 or 2, wherein the conductive particle has a protrusion on the outer surface of the conductive portion. 4. The conductive particle according to any one of claims 1 to 3, comprising an insulating material disposed on an outer surface of the conductive portion. A conductive material comprising the conductive particles according to any one of claims 1 to 4 and a binder resin. A first connection object member,
A second member to be connected,
And a connection unit connecting the first connection target member and the second connection target member,
Wherein the connecting portion is formed of the conductive particles according to any one of claims 1 to 4 or formed of a conductive material including the conductive particles and the binder resin.

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